WO2005073140A1 - Compositions de verre ameliorees - Google Patents

Compositions de verre ameliorees Download PDF

Info

Publication number
WO2005073140A1
WO2005073140A1 PCT/GB2005/000191 GB2005000191W WO2005073140A1 WO 2005073140 A1 WO2005073140 A1 WO 2005073140A1 GB 2005000191 W GB2005000191 W GB 2005000191W WO 2005073140 A1 WO2005073140 A1 WO 2005073140A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
enamel
pigment
glass composition
composition according
Prior art date
Application number
PCT/GB2005/000191
Other languages
English (en)
Inventor
Geert Klass Bentem
Reinout Jozef Nikolaas Aloys Matthias Kicken
Detlef Rehorek
Original Assignee
Johnson Matthey Public Limited Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Johnson Matthey Public Limited Company filed Critical Johnson Matthey Public Limited Company
Publication of WO2005073140A1 publication Critical patent/WO2005073140A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/02—Compositions for glass with special properties for coloured glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/119—Deposition methods from solutions or suspensions by printing

Definitions

  • the present invention provides an improved glass composition, more especially an improved glass frit composition, having uses in preparing enamels.
  • frit powdered glass
  • Frits can be prepared by rapid cooling of molten glass, usually by pouring a stream of molten glass into a bath of water, recovering the resulting glass granules and grinding to a desired particle size. Frits are used as a melting component in admixtures with ceramic pigments; such a mixture is termed an enamel.
  • the enamel may be applied as artistic or functional decoration to substrates capable of withstanding firing or heat treatment to the temperatures at which the frit becomes molten.
  • substrates include ceramics of most types, glass surfaces, metal surfaces, glazed ceramics or metals.
  • the enamel is usually applied in the form of a fluid composition of enamel admixed with a liquid suspension medium, especially a fugitive organic medium, to form an ink by screen printing onto the substrate.
  • a liquid suspension medium especially a fugitive organic medium
  • Alternatives include manual brushing and applications by machine including offset printing.
  • a variant comprises applying the enamel ink onto a carrier such as a release paper, for example gummed paper, to form a decal and the decal is then applied to the substrate.
  • a ceramic pigment is a pigment that is heat stable at the temperature at which the enamel is fired, that is at the temperature at which the glass frit component melts. Ceramic pigments are not necessarily heat stable under normal glass melting temperatures and under conventional conditions.
  • enamel inks are to form, by screen printing, a black obscuration band on automotive glass.
  • the automotive glass is held in position in the vehicle by an adhesive.
  • the general requirements for such enamels is that they should be opaque in order to prevent degradation of the adhesive by sunlight and not cause sticking to tools used in the handling or forming of the glass sheets.
  • the enamel is free of toxic elements such as Pb and Cd;
  • the enamel should not form strong visible light absorbing or light scattering species. That is, the recycled glass should be transparent to visible light. Of course, this requirement is much more important for flat glass made from recycled components, than for bottle or other container glass. It should also be noted that if melting or recycling is carried out under a reducing atmosphere, there is a greater tendency for coloured species to form.;
  • the components of the enamel must not lead to excessive interaction with/destruction of the refractory material used to line the glass furnace or the glass handling components;
  • the enamel must not contain Ni, since nickel sulphide stones may form in the glass melt, which can cause spontaneous glass breakage of tempered float glass.
  • attack on ceramics in glass furnaces includes the so-called "hole-drilling" by metals. This can happen, for instance, with easily reducible metal ions (eg: Bi 3+ ) when reduced to their elemental form. Such metals react with the refractory ceramic lining of the furnace to form a hole that is impossible to repair without a furnace rebuild. Fluorides are other components that have a negative effect on the lifetime of the furnace.
  • the enamel has to meet the technical requirements set by the automotive manufacturer.
  • the present invention provides a glass composition that is particularly suitable for forming a component of recyclable enamels.
  • a glass composition comprises 35-45 wt% SiO 2 , 12-20 wt% B 2 O 3 , 10-16 wt% ZnO, 0-12 wt% Na 2 O , 1-15 wt% K 2 O, up to 2 wt% Li 2 O, provided that Na 2 O + K 2 O + Li 2 O is in the range 10-15 wt%, 8-18 wt% TiO 2 , up to 2 wt% CaO, up to 1 wt% SrO and up to 5 wt% BaO, provided that CaO + SrO + BaO is in the range 0.4 to 5 wt%, and which composition is preferably essentially free of fluoride.
  • the glass composition may comprise additional components, perhaps by way of contamination, totalling no more than 2 wt% of each of ZrO 2 , Fe 2 O 3 , MnO, MgO, SnO 2 , La 2 O 3 , CeO 2 , P 2 O 5 , N 2 O 5 and sulphur.
  • small amounts of fluorides may be used as raw materials.
  • the glass composition should be fluoride-free as a deliberately added component.
  • the glass composition is desirably in the form of a frit.
  • a frit according to the invention may also be composed of a blend of frits having the glass composition according to the invention
  • the glass composition may comprise one or both of Al 2 O 3 in an amount up to 3 wt% and Bi 2 O 3 in an amount up to 5 wt%.
  • the glass composition is essentially free of Bi 2 O 3 .
  • the glass composition is essentially free of SnO 2 .
  • the invention further provides a ceramic colour composition, or enamel, comprising at least one glass composition according to the invention and at least one ceramic pigment.
  • the enamel does not contain components that prevent recyclability.
  • Ceramic pigments are commercially available from a number of sources. For the preferred use of recyclable enamels, however, the choice of pigments is restricted.
  • the pigment in the enamel is dissolved in the glass melt.
  • the coloured transition metal ions that form the pigment are then incorporated into the glass structure.
  • the dissolved pigment contributes to the light absorption of the final glass, eg float glass.
  • Elements such as Cr, Co and ⁇ i - form light absorbing species regardless of their oxidation state.
  • Cu can be reduced to colourless ions such as Cu(I) ions, but Cu(I) is unstable and disproportionates to give colloidal elemental Cu that reduces the light transmission of the glass. Therefore, the Cu content in the pigments should also be kept low.
  • Iron compounds are normally added to the glass batch for making float glass. No problems are therefore anticipated if the pigment contains iron compounds.
  • Manganese ions form coloured glasses if the oxidation state is >2, whereas Mn(II) ions hardly contribute to visible light absorption. Pigments containing Mn compounds do not cause problems for recycling.
  • Magnetite see eg DE 44 01 657
  • pigments based on iron-manganese mixed oxides are known to form black glass enamels.
  • Pigments with this composition are commercially available, eg: Bayferrox 303 manufactured by Bayer Ag or Black 10G930, manufactured by Shepherd Color Company.
  • the heat stability of magnetite pigments may be improved by coating with a glass composition (see DE 195 25 658).
  • Enamel powders are preferably made by dry blending of a frit powder with one or more pigment powders. Co- wet milling of the unground frit with the pigment may alternatively be used, or calcining a frit-pigment blend, followed by milling may also be used for making the enamel powder.
  • the amount of pigment in the enamel powder is typically from 10 to 30 wt%, preferably from 15 to 25 wt%.
  • the invention also provides an ink suitable for application to glass, comprising an enamel according to the invention, suspended in a suitable fugitive medium, eg: a screen printing medium.
  • a suitable fugitive medium eg: a screen printing medium.
  • the ink can be manufactured by mixing the frit and pigment powders and dispersing the enamel in the chosen medium using three-roll milling or by alternatives such as bead-milling or high-speed mixing.
  • the resulting paste may be diluted, if necessary.
  • a screen-printing paste has a viscosity of from 5 to 25 Pas (at a shear rate of 10s "1 ).
  • the media used to make the ink are commercially available, eg: from the Johnson Matthey group and may be an IR-drying medium such as 650-63, 700-63 or 702-63, a UN-curable medium such as 660-70 or 724-70 or a thermoplastic medium such as 64-64.
  • Suitable particle sizes for the glass frit are from 6 to 18 ⁇ m.
  • Suitable particle sizes for the pigment are from 1 to lO ⁇ m, preferably from 1 to 5 ⁇ m.
  • the properties of the ink may be chosen according to the specific application method, firing schedule, etc, by routine experiment and optimisation.
  • the ink may be applied to automotive glass by screen printing, but alternative methods may be used.
  • an ink suitable for inkjet printing may be formulated and we incorporate the teaching of UK patent application No 0327340.6 (CBG1644) herein.
  • Suitable printing parameters and firing schedules are known in the art.
  • Glass samples Nos 1-11 The appropriate precursors in the form of oxides, borates, fluorides, phosphates or other suitable precursor, are mixed together, melted at approximately 1200°C for about 1 to 1.5 hours, then quenched by discharging into a flow of cold water to form a glass frit.
  • Table 1 shows glass compositions in wt%. The frit may be ground into a powder, for example by ball milling or jet milling. Glass samples 3 and 11 are for comparative purposes, and are not according to the invention. Table 1
  • Tg glass transition temperature, measured by Differential Scanning Calorimetry.
  • CTE coefficient of thermal expansion
  • Acid resistance was measured according to ASTM C724-91 on a scale of 1 to 7, with 1 indicating no attack and 7 indicating total dissolution.
  • frits Nos. 12 to 15 were formulated into enamels Examples Nos. 1 to 4 as set out in Table 4 below. Although frit 15 is not according to the invention, it may be blended together with one or more other frits to yield a frit according to the invention. Table 4 - Enamels

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne une composition de verre destinée à la formation d'une fritte, qui comprend du SiO2, du B2O3, du Zn0 et du TiO2, ainsi que des doses minimes d'autres composants. La fritte de verre combinée à certaines couleurs céramiques peut former des encres conçues pour l'impression sur du verre automobile qui peut être recyclé à la fin de la vie du véhicule.
PCT/GB2005/000191 2004-01-30 2005-01-18 Compositions de verre ameliorees WO2005073140A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0401918.8 2004-01-30
GB0401918A GB0401918D0 (en) 2004-01-30 2004-01-30 Improved glass compositions

Publications (1)

Publication Number Publication Date
WO2005073140A1 true WO2005073140A1 (fr) 2005-08-11

Family

ID=31971651

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2005/000191 WO2005073140A1 (fr) 2004-01-30 2005-01-18 Compositions de verre ameliorees

Country Status (2)

Country Link
GB (1) GB0401918D0 (fr)
WO (1) WO2005073140A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7560401B2 (en) 2007-04-20 2009-07-14 Johnson Matthey Public Limited Company Frits and obscuration enamels for automotive applications
WO2013175435A1 (fr) * 2012-05-24 2013-11-28 BSH Bosch und Siemens Hausgeräte GmbH Procédé de revêtement céramique d'un métal
US8894872B2 (en) 2007-09-24 2014-11-25 Dip Tech Ltd. Etching compositions, methods and printing components
CN110305523A (zh) * 2019-07-02 2019-10-08 黄山市晶特美新材料有限公司 一种丝印抗冲击玻璃油墨及其制备方法
EP3448819B1 (fr) 2016-04-27 2020-03-04 Saint-Gobain Glass France Procede d'impression d'email pour vitrage feuillete a couches fonctionnelles.
EP3242915B1 (fr) 2015-01-07 2021-09-08 Fenzi SPA Composition de fritte de verre et encre pour impression jet d'encre sur céramique la comprenant
GB2602696A (en) * 2020-10-16 2022-07-13 Fenzi Agt Netherlands B V Enamel paste compositions, enamel coated products, and methods of manufacturing the same
WO2022225391A1 (fr) * 2021-04-21 2022-10-27 Fenzi Agt Netherlands B.V. Compositions de pâte d'émail, produits revêtus d'émail et leurs procédés de fabrication

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0535474A2 (fr) * 1991-10-01 1993-04-07 Flachglas Aktiengesellschaft Procédé de fabrication d'un vitrage feuilleté bombé simplement ou bombé doublement, notamment pour véhicules automobiles
WO1996030450A1 (fr) * 1995-03-24 1996-10-03 Ford Motor Company Peinture a base d'eau pour feuilles de verre
JP2002179435A (ja) * 2000-12-11 2002-06-26 Asahi Glass Co Ltd ガラス、セラミックカラー組成物およびセラミックカラー層付ガラス板

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0535474A2 (fr) * 1991-10-01 1993-04-07 Flachglas Aktiengesellschaft Procédé de fabrication d'un vitrage feuilleté bombé simplement ou bombé doublement, notamment pour véhicules automobiles
WO1996030450A1 (fr) * 1995-03-24 1996-10-03 Ford Motor Company Peinture a base d'eau pour feuilles de verre
JP2002179435A (ja) * 2000-12-11 2002-06-26 Asahi Glass Co Ltd ガラス、セラミックカラー組成物およびセラミックカラー層付ガラス板

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 2002, no. 10 10 October 2002 (2002-10-10) *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7560401B2 (en) 2007-04-20 2009-07-14 Johnson Matthey Public Limited Company Frits and obscuration enamels for automotive applications
US8894872B2 (en) 2007-09-24 2014-11-25 Dip Tech Ltd. Etching compositions, methods and printing components
WO2013175435A1 (fr) * 2012-05-24 2013-11-28 BSH Bosch und Siemens Hausgeräte GmbH Procédé de revêtement céramique d'un métal
EP3242915B1 (fr) 2015-01-07 2021-09-08 Fenzi SPA Composition de fritte de verre et encre pour impression jet d'encre sur céramique la comprenant
EP3448819B1 (fr) 2016-04-27 2020-03-04 Saint-Gobain Glass France Procede d'impression d'email pour vitrage feuillete a couches fonctionnelles.
US11207875B2 (en) 2016-04-27 2021-12-28 Saint-Gobain Glass France Enamel printing process for a laminated glazing having functional layers
CN110305523A (zh) * 2019-07-02 2019-10-08 黄山市晶特美新材料有限公司 一种丝印抗冲击玻璃油墨及其制备方法
GB2602696A (en) * 2020-10-16 2022-07-13 Fenzi Agt Netherlands B V Enamel paste compositions, enamel coated products, and methods of manufacturing the same
WO2022225391A1 (fr) * 2021-04-21 2022-10-27 Fenzi Agt Netherlands B.V. Compositions de pâte d'émail, produits revêtus d'émail et leurs procédés de fabrication

Also Published As

Publication number Publication date
GB0401918D0 (en) 2004-03-03

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